Bacteriostatic cleansing compositions



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United States Patent Patented Mar. 28, 196i ice ostatic properties. Itis also an object of this invention to provide uch BACTERIOSTATICCLEANSING COMPOSITIONS a cleansing composition that exhibits highlydesirable Wilbur s- Taylor, Norwalk Conn assign to R T. eztlteticprfopfirties grortn the standpoint of consumer ac. Vanderbilt (10.,Incorporated, New York, N.Y., a corc P i 0 e pro r 4 Duration of NewYork It is a further ob ect of this invention to prov de a method ofinhibiting the formation of body odors.v No Drawing. Filed Apr. 21,1958, Ser. No. 729,567 g V I have found that amine complexes of zincdime thyldi- 9 Claims. (Cl. 252 107) thiocarbamate as a classincorporated in cleansing compositions have properties comparing veryfavorably with former compounds used for this purpose and that infactsome of the amine complexes are considerably better This inventionrelates to new and useful improve- 5 than the previously used andreported compounds. The ments in bacteriostatic cleansing compositionsand more use of-these cleansingcorhpositions will retard the growthparticularlyhas for its aim to provide amine complexes of body bacteriaand'inhibit formation of bodyodors of zinc dimethyldithiocarbamate asthe active agent in, over a longlpe'riod'oftime. V 7 i bacteriostaticcleansing compositions. The present invention is not concerned with themeth- Many compounds are known that have bacteriostatic ods of preparingtheQamine complexes which are deproperties against specific bacteria orgroups thereof. scribed in patents and other literature, e. g., Patent-Nos. However, such a property may be destroyed or seriously. 2,208,327(Lichty) and12,805,996 (Deger). Generally impaired when the specificcompound is incorporated into the complexes are prepared by bringingtogether the cleansing compositions, which generally include deteramineand zinc dimethyldithiocarbama'te in the presense gents. of a reactiondiluent such as gasoline, water or alcohol. One soap presently on themarket contains tetramethyl- Although these amine. complexes, havepreviously been thiuram disulfide and another contains bis(Z-hydroxydescribed, their exact structure is not shown.3,5,6-trichlorophenyl) methane (commonly known as The specificprocedures used to test the properties hexachlorophene). Quinn et al.,at 2 Applied Microbihereinbefore enumerated are described here in somedeology 202-4 (1954), have discussed a method of evalutail. 'Afterpreparation of the particular amine complex, ating bacteriostatic ormedicated soaps and have included 0.5 %'and 1% thereof was blended withX brand soap hexachlorophene and closely related compounds, sodi and/orZ .brand soap. representing two kell-known um pentachlorophenate andzinc dimethyldithiocarbamate proprietary soaps which do not containbacteriostatic as bacteriostatic agents. agents. In addition, 0.5% ofeach amine complex and The retention of bacteriostatic properties by acom- 39 0.5 2,6 ditertiary-butyl-{l-methylphenol (a commercial poundafter inclusion in a cleansing composition is only stabilizer underthetrade narne Vanlube PC) mixture one of the necessary or desirableproperties the com- Was blended with each soap. 7 a I pound must have tobe considered as a desirable addi- Bacteriostatic activity per se wastested by taking soap tive to the cleansing composition. It is extremelyimplugs of the blended soap ribbons and plating them on portant that thecompound exhibit substantivity, i.e., the separate nutrient agar platesinoculated with Bacillus property of remaining on the skin and retainingbacterisubtilis (found in soil and decomposing organic material),ostatic activity over a period of time after washing and Micrococcuspyogenes var. aureus (found on the human rinsing of the skin. skin) andSalmonella typhosa (cause of typhiod fever). Other properties that arenot concerned with the bac- These three bacteria are conventionally usedin in vitro teriostatic properties directly are, however, important astesting for activity and U Y YJ The plates were far as commercial use ofthe cleansing composition by incubated for 24 hours at about 37C. andthen the the general public is concerned. These include the foldiamefiirf the-Z0116. o I10 bacterial growth und the lowing properties of a soapbar,'powder, etc. after in- P g t f m etcrs and recorded. clusion of thespecific compound: 5O Substantivny wasmeasured by soaking untannedj calfskin buttons in an 8% solution of the test soap, then (1) Imtlalwhliefless repeatedly rinsing the buttons in distilled water, and sub-(2) Color f f under f h exposure sequently placing the buttons onnutrient agar plates-in- (3) C0101 slablllty under aging oculat'edhwiththe same bacteria as noted above. fThere-f Discolol'ation y pp Presentin stamplng d after, the procedure is the same as followed for bacteri-(5) Effect on copper (present in plumbing fixtures) i i i pepse. in j(6) Discoloration by water ofv high iron content The following tableshows the. bacteriostatieactivity (7) Skin irritation and substantivityresults: 7 TABLE I i 17 Amine Complex Activity -Substantlvity N0. SoapVP C V I Name .Per- S A T S A T cent X No. None (contro1) Tr Tr 5 0 0 0X Yes. 0 0 0 0 0 0 Z 0 0 0 0 0 0 Z Tr Tr 0 0 0 '0 z 0 Tr Tr 0 0 0 z 0 TrTr o 0 o X M 26 1s 24 9 a 6 s X 26 18 22 Tr 2 4 x 1 30 20 24 10 4 s z 342s 18 24 12 3 8 Z 18 22 9 4 .1

4 is the deepest color 04 353.16.16 .84323 .9005? 9002? 22 .4r.631683824583r62r2422r334265r1221236222844757 1 T T n n H T A T" T T T Ty t W .1 t 4651 I1 I r r r 1r 5 1 5 n 42 32222 40022 4O0 0 2 222344W4418552422264 0524664. T1222 3 y232243 a r f. M U 678264056 .47662.40r67 .20. .8r 85 .90 630067084744265126621848529r1244248112624229 s 11 1 1 T 1 T T u n 111 1 l 1 T 1.1 1 61803FJ3 -5683OD 67606 00 0809772886340322901504220957165584686658868911 2323222 31132 21122 33 4.12222211222222212222223222222.2212221222122223 v. u H 0 u t .1 0644009-85624 7492 55 a 65 866286064584569 d267666822069247534666604 W 222222111121 1111M M11 MIN NQZM1112222222122212221229.122211221222122???- n n nn A 088099 71064 40 00 22 2 3675080636 5280656867876660544585563288988891 1 1 t S 333422 22232 22232 22 2223333233333333333323332333333323332333233323 n n n 2/ -2 0-2 20L 2 01 aP2 22 nln 22 22 2 P nu 22 22 2 2 2 22 2 2 V17 V/ 1/V/ 1 V/ /v& A/ flV/V/ V/% AV m 1 1 1 1 1 11 1 M1 1 V/V VV /V V// yV yV V. yy 1/ 1 11 1111 11 1 111 PC tense color as 4. The colors developed are indicated inTable II. 0 is the White of the control bar; 1 is the first control bar;2 is the next shade of off-white deeper than 1 3 is the next shadedeeper than 2 noted.

.The sunlight color stability was tested by breaking a 75 soap bar inhalf and exposing one-half in an east window TABLE I-Continued a m .m. Hm H mm & u 0 e c e u w .m. e m n H. .B. D. .m. 8 m a "n" I: m N .W. 1 O1W m 0 .m m .m A m. .H. m. m 0 n "W W n u h m N "v. n m m n n.um um w nno 0 plus v .1 6 e. .y. ...1 ..V.. we we o mo a adame 0 one a a am a m aA Ame H TKI. C 1 :A. N T. 1515:; 5 Is 1 09 0e 000 00080008 e 009 NY NYNNNYNNNYNNNY Y NNY NO. Soap VPC VPC2,fi-ditertiary-butylt-methylphenol.

S-Bacillus subtz'lis.

A-Micmcoccus pyogenes var. aureus.

lvfethy l %imate-Zinc dimethyldithloearbamate.

Methyl Tuads-Tetramethylthiuram disulfide. East.--Eastman Kodak (sourceof atom R. & H.Rohm & Haas (source of amine).

Egg; }Propietary soaps containing no bacterlostatlc agent.

Thus it is obvious from the results reported in Table I that the aminecomplexes of zinc dimethyldithiocarbamate exhibit both bacteriostaticactivity and substantivity; shade of oil-white distinguishable from thewhite of the Various other desirable properties of the same soap-amineThe initial whiteness is rated visually as intensity of color, the shadeof the control rating 0 and the most 111- Key to Table I:

complex mixtures of Table I are reported in following tables.

for two weeks, the exposed half-bar'beingfiotated oriequarter turndaily. Color darkening comparedwith the color of the unexposed half ofthe control bar (held in a closed opaque box at room temperature for thesame period) was rated visually from to 4 by half increments. 0 may ormay not be white as it represents the soap'from the initial whitenesstest, e.g., soap No. 6

ings were then assigned in the same manner as for the sunlight test with6 being the deepest color noted. The Z brand soaps develop yellow andgreen shades in this test which are so recorded.

The eifect of a high iron content in water was tested by placing a halfbar of soap flat 'in an open petri dish with sufficient water to coverthe lower portion of the half bar. The water contained 1 ppm. of irondue to addition of the calculated amount of FeCl .4H O, except forsamples 5, 6, 13-19, and 47-55 wherein the water contained ppm. as aresult of dissolving FeCl .6H O in distilled water. The effect of ironwas not tested on samples 57 through 89. Visual ratings of color changewere assigned after the water had evaporated, O indicating no changefrom the color of the bars unexposed to iron, and 1 through 4 indicatingincreasingly dark shades to coppery red.

No skin irritation has been noted with any of the amine complexestested.

sample number being retained from Table I but the amine names omittedfor convenience of space.

TABLE II a a -4 a 5 3 a Y 4 o 2 YG 2. 1 YG 3. a YG 1. 3 o. 1 1. 2 2. aY 1. 2 Y p 1. a Y 3 o. 1.5 2 0. 1.5 a o. 2.5 a o. a GY 1 o. 2 GY a o. aGY 1. a 1. 3 1. a 2 3 2 2 1 1 NMPOOOOOOLOHHOOOHHPOGONMMNHHOJDPWNWLbIhOQODhWWNi-OOQO Initial Heat Iron No.White- Sunlight Aging Water ness- 2 P 2 3 2 P 1 3.5 1 P 1 3.5 2 P 2 2 2P 2 3 l P 1 2.5 2 G 2 3.5 2 G 2 3.5 2 G 2 p 3.5 2 C 2. 2. 2 C 2 2.5 2 22.5 11? 2 2.5 1 C 2 .4 '1 2 .5. BY 1 ....5 3Y 2 .6. .2Y 1 ...6

1 2 .5, .1 2 2.. 2 2. 1 1. 1.5.. 1 .2 ,2, 2 .1 .2 1 P 2 r 2 1' 2 V 3 2,1 4 V 1 P 1 V 1.5 1 P 1 2.5

Key to Table II:

'.lrTrace, less than 0.5 in shade. C-Cream. GGreen.

PPink.

It will be noted thatisoaps 20 to 8 9 with the amine complexes comparevery favorably with and in many Table II gives the results of the abovetests the 35 instances are superior'l'o either the sgap S i to: withzinc dimethyldithiocarbamate or soaps 16 to 19 with tetramethylthiur'amdisulfide for all Of the discoloration features reported. It will beappreciated, of course, that several of the discoloration featuresreported in Table II such as initial whiteness, sunlight aging and shelfaging, can be counteracted by coloring the soap bar which is done withvarious commercial soaps.

Copper sensitivity as manifested by the staining of-the soap bar is adefect which cannot be overcome by .coloring the bar. More importantthan the discolorationof V the soap bar is the cumulative deterioratingeffect of the soap ingredientsupon the copper-bearing plumbing andfixtures. Continued use of-soaps containing these coppersensitiveingredients leads to discoloration of and damage f to the plumbing andfixtures. In order to evaluate the effect of contact of copper withsoap, a copper sensitivity test was devised. Bars of 2" brand soapselected on the basis of activity and substan- 1 tivity as reported inTable I were subjected to intimate contact with copper in the followingtest.

Test bars were prepared by scraping to provide a clean surface, thenplaced in contact with a clean strip of copper and held for two weeks atroom temperature in a glass dish covered with Pliofilm brand plastic. Asmall amount of water was placed in each dish out of contact with soapor copper to provide a humid atmosphere. 7

Conditions more nearly simulating those of actual use were then applied.The test soap bars were wetted with .-distilled water to thus emulsifythe surface, the copper of staining after brush scrubbing and drying.The

severity of the stain on thesoap bars is reported from 0. (no stain) to10 (the greatest stain) and the particular i color of stain described.The stain on the copper strip after cleaning is reported as 0 (no stain)to 5 (verydeep' the soap and the copper strips were examined forevidence brown). The staining on either the soap or copper strip occursonly in the area where they are in contact.

TABLE III Copper sensitivity Copper on Soap Soap on No. Copper,

Amount Color Amount Green and violet Green and gray Brown .d Chocolatebrown d Tan purple Grcenish chocolate Bluish violet Grecnish brown...Bluish brown. Purplislr tan The results of the copper test as reportedin Table III show that the amine complexes cause less stain on soap andfar less stain on copper than either the zinc dimethyldithiocarbamate orthe tetramethylthiuram disulfide. This is a particularly importantfeature in view of the relative permanency of the plumbing fixtures.

The specific examples reported by way of the tables herein aboveincluded 0.5 to 1% by weight of the amine complex in the soap bar inorder that specific comparisons could be made with the various complexesand also with various controls and prior art compounds. However, it willbe obvious that a wider range of amine complex can be used and I havefound from 0.2 to to be generally a satisfactory range although thisshould not be a limiting feature on my invention.

Although it is not necessary for the success of this invention, it willbe noted that the stabilizer 2,6-ditertiarybutyl-4-methylphenol enhancesthe color stability and reduces the copper sensitivity of many of theamine complexes when used in soap, particularly the tertiaryoctylaminecomplex. The desirable range of this stabilizer is about 0.05 to 0.5% byweight of the soap.

It would appear from these results that the amine complexes of zincdimethyldithiocarbamate have properties that will permit their use as aningredient of a bacteriostatic or medicinal soap. It is furthermore truethat the more successful complexes are derived from primary andsecondary monoamines and diamines. The most successful amines of thetested complexes appear to be tertiery-butylamine, menthanediamine,dimethylaminopropylamine, hydrazine, N-ethylcyclohexylamine andtertiaryoctylamines, including l,l,3,3-tetramethylbutylamine.

It will be appreciated that the zinc dimethyldithiocarbamate alone is afairly successful agent, particularly in regard to bacteriostaticactivity and substantivity. In fact it is better in these two propertiesthan tetramethylthiuram disulfide and hexachlorophene that are beingused commercially at the present time. However, the zincdimethyldithiocarbamate amine complexes are generally less sensitive inthe copper tests than zinc dimethyldithiocarbamate alone. Furthermore,they have excellent original color in the soap bar. Both of thesefeatures are highly desirable and dictate the choice of the complexesfor commercial product exploitation.

It is well known, that one of the desirable properties of abacteriostatic soap is the inhibition of body odors over a period oftime. Soaps incorporating the amine complexes of this invention serve inthis same respect to inhibit body odors over a period of time.Furthermore, the complexes may be incorporated into cleansingcompositions other than ordinary soaps such as the regular liquid, solidor powdered deodorants which are used primarily to inhibit body odorsrather than for the removal of foreign materials from the body surface.

Generally the body deodorants on the market today include astringent andneutralizing compounds. The astringent compounds tend to close the poresof the sebaceous glands so as to reduce perspiration. The neutralizingcompounds tend to mask the odor, prevent formation of ill-smellingcompounds, or react therewith to chemically change them. Actually thefreshly secreted product from the sebaceous glands is not consideredillsmelling but instead the odors are caused by decomposition products,the decomposition being caused by bacteria.

Therefore, control of the body bacteria as exemplified by the examplesherein serves to inhibit the formation of body odors. Most any commonsoap will reduce or destroy body odors at the time of application butsubstantivity is required if the odor-free condition is to be maintainedover any period of time.

The amine complexes of this invention may be incorporated then in soaps(conventional cleansing soaps or cleansing detergents generally) orvarious other bases used to maintain personal hygiene by reducing bodyodor and cleansing compositions are used generically herein to includeall bases that may be used for personal hygiene in reducing body odors.In fact, the amine complexes can be applied directly to the skin withouta base to inhibit body odors if desired.

I claim:

1. A bacteriostatic cleansing composition comprising soap and an aminecomplex of zinc dimethyldithiocarbamate.

2. A bacteriostatic cleansing composition comprising soap and 0.2 to 10%by weight of an amine complex of zinc dimethyldithiocarbamate, saidamine being selected from the group consisting of cyclohexylamine,1,l,3,3-tetramethylbutylamine, ethylenediamine, 2-methoxyethylamine,pyrrolidine, morpholine, tertiary-octylamine, triethylenetetramine,aminoethylethanolamine, dimethylaminopropylamine, hydrazine,N-aminopropylmorpholine, N-ethylcyclohexylamine, diallylamine,tertiarybutylarnine, and menthanediarnine.

3. A bacteriostatic cleansing composition as claimed in claim 2 thatalso contains 0.05 to 0.5% by weight of2,6-ditertiary-butyl-4-methylphenol.

4. A bacteriostatic cleansing composition as claimed in claim 2 whereinsaid amine is 1,l,3,3-tetramethylbutylamine.

5. A bacteriostatic cleansing composition as claimed in claim 2 whereinsaid amine is tertiary-butylamine.

6. A bacteriostatic cleansing composition as claimed in claim 2 whereinsaid amine is menthanediamine.

7. A bacteriostatic cleansing composition as claimed in claim 2 whereinsaid amine is dimethylaminopropylamine.

8. A bacteriostatic cleansing composition as claimed in claim 2 whereinsaid amine is hydrazine.

9. A bacteriostatic cleansing composition as claimed in claim 2 whereinsaid amine is N-ethylcyclohexylamine.

(References on following page) References Cited in the file of thispatent OTHER REFERENCES UNITED STATES PATENTS Bechtold: D. and C. Ind.,78:3, March 1956, pp. 326,

327, 402. Stewart Mar. 11, 1952 Fishburn: The Chemist and Druggist, vol.148, October Lipsitz Oct. 26, 1954 5 4, 1947, p. 415.

Quinn: Applied Microbiology, 1954, pp. 202-4.

UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent Nd.237K316 March 28 1961 Wilbur S. Taylor It is hereby certified that errorappears in the above numbered patent requiring correction and that thesaid Letters Patent should read as corrected below.

Column l, line 54 before "present" insert; an opening parenthesis;column 2 line 24 for "presense" read presence line 32, for "kell-known"; read me well-known column 3 line 67 for "Propietary" readProprietary column 7 line 416 for "above" read have Signed and sealedthis 29th day of August 1961.

(SEAL) Attest:

ERNESTW. SWIDER DAVID L; LADD Attest-ing Officer v Commissioner ofPatents

1. A BACTERIOSTATIC CLEANSING COMPOSITION COMPRISING SOAP AND AN AMINECOMPLEX OF ZINC DIMETHYLDITHIOCARBAMATE.